Sulfuric acid bleaching of kraft pulp 1: Bleaching of hardwood and softwood kraft pulps

To develop a new nonchlorine bleaching technology, hardwood and softwood kraft pulps, before and after oxygen-alkali predelignification, were treated with dilute sulfuric acid solutions (pH 1.0-1.8) at 100°C for 1 h and then extracted with aqueous sodium hydroxide at 70°C for l h. Hardwood kraft pulp was successfully bleached. The delignification selectivity was similar to that seen with oxygen-alkali bleaching; and it was greatly enhanced by the addition of sodium nitrate and sodium nitrite. The sulfuric acid bleaching can replace the presently adopted oxygen and chlorine stages if the additives are allowed. This bleaching process was also effective for oxygen-bleached hardwood kraft pulp, but it was less effective for softwood kraft pulp and oxygen-bleached softwood kraft pulp. The effectiveness of the addition of sodium nitrate and sodium nitrite was more apparent for softwood kraft pulp than for hardwood kraft pulp.Part of this report was presented at the 7th International Symposium on Wood and Pulping Chemistry, Beijing, July 1993     

Response of <Emphasis Type="Italic">Eucalyptus camaldulensis</Emphasis> and <Emphasis Type="Italic">Acacia mangium</Emphasis> kraft pulp in different ECF bleaching options

In this study, the response of Eucalyptus camaldulensis and Acacia mangium kraft pulp to different options of ECF bleaching was investigated. Oxygen-delignified pulps of both species having similar kappa number (c.a. 12) were used. Both the pulps were prebleached using conventional ClO₂ stage (D₀), combined use of ClO₂ and O₃ (DZ), hot acid treatment before D₀ (A_hotD₀) and hot acid treatment before (DZ) i.e., A_hot(DZ), hot ClO₂ treatment (D_HT) and A_hot followed by D_HT (A_hotD_HT). All prebleached pulps were finally bleached to 90%+ ISO brightness using D₁ option. The overall benefits of other options were not considerable compared to D₀ and (DZ). From the ClO₂ consumption point of view, for a certain species, the option A_hot(DZ) was the best. Instead of D₁ in final bleaching, pressurized hydrogen peroxide (PO) was also investigated in the case of D₀ and (DZ) prebleached pulps. (PO)-bleached pulp produced higher brightness stability but lower viscosity compared to D₁.     

氧漂过程中脱木质素与木质素氧化之间定量关系的研究

对氧碱漂白过程中木质素氧化进行定量分析,分析方法是基于氧化前后高锰酸钾消耗量的变化。该方法对溶出残余木质素的氧化结果分析发现其呈明显3个阶段：第一段木质素氧化的当量电荷数约4～5／木质素单元;木质素总氧化电荷数大约为9／木质素单元。这些数据以及甲氧基的脱除（75％）均表明：木质素的氧化不仅发生在酚型木质素单元,同时也发生在非酚型结构单元上。只有第一阶段氧化反应是木质素与氧气直接反应,而在第二、三阶段主要是协同氧化作用,氧化反应过程中产生的活性氧基团扮演了一定角色。通过对低浓度针叶材硫酸盐浆的氧漂研究发现：当卡伯值下降一半（25．4至13．4）时平均每个木质素单元氧化3当量电子,氧漂后的纸浆中仍然有大量未被氧化的残余木质素。定量地证明了在氧漂过程中木质素氧化是脱木质素反应的实质。     

Sulfuric acid bleaching of kraft pulp II: Behavior of lignin and carbohydrate during sulfuric acid bleaching

The purpose of this study was to investigate the behavior of lignin and carbohydrates in kraft pulps during sulfuric acid bleaching. Beech kraft pulp and red pine kraft pulp were bleached with dilute sulfuric acid at pH 1.3 with addition of sodium nitrate and sodium nitrite at 100°C for 1 h. The pulps were then extracted with aqueous sodium hydroxide solution at 70°C for 1 h. Lignin and carbohydrates in the acid effluents and the alkali effluents were analyzed. The carbohydrate compositions of unbleached and bleached kraft pulps were also determined. The residual lignin in kraft pulp was degraded to a molecular size similar to that of milled wood lignin during sulfuric acid bleaching without additives, and it was further degraded to a much smaller molecular size during sulfuric acid bleaching with additives. It was found that the amount of carbohydrate dissolved in the bleach effluents were only about 1 of the dry weight of the kraft pulp under these bleaching conditions. The carbohydrates dissolved during bleaching were mostly of hemicellulose origin.Part of this report was presented at the 8th International Symposium on Wood and Pulping Chemistry, Helsinki, July 1995     

DMD的活化预处理及其全无氯漂序的研究

研究了桉木硫酸盐浆对氧脱木质素段和过氧化氢漂段的活化作用以及ＤＭＤ用量对氧段和过氧化氢段浆性能的影响,使经ＭＯＱＭＰ多段漂白的纸浆最终白度达８０％以上,纸浆粘度满足要求,可以实现桉木硫酸盐浆的全无氯漂白。     

硫酸盐竹浆氧脱木质素和全无氯漂白的研究

通过比较不同条件下氧脱木质素后浆料的卡伯值、黏度、得率、白度和脱木质素选择性等指标,研究了硫酸盐竹浆卡伯值25.6氧脱木质素工艺参数,发现用碱量和温度是决定氧脱木质素效果的主要因素.最佳工艺条件为:用碱量3.5%,温度85℃,氧气压力0.6MPa,保温时间80min.两段氧脱木质素(中间不洗涤)可以提高木质素脱除率和选择性.研究还发现,在氧碱脱木质素过程中加入醌类混合物助剂(表示为Oq),可使浆料的黏度和氧脱木质素的选择性大大提高.采用OQ(PO)、(O1O2)Q(PO)、OQ(PO)1(PO)2和OqQ(PO) 4种短漂序都可使竹浆白度达到80%(ISO) 以上,且具有很好的白度稳定性.OQ(PO)、(O1O2)Q(PO)和OQ(PO)1(PO)2 3种漂序漂后浆纸页强度性能相近,OqQ(PO)漂后浆的抗张指数、撕裂指数和耐破指数明显高于其它3种漂序.     

竹子深度脱木质素蒸煮与常规硫酸盐法蒸煮的比较

为了提高竹浆性能和减少环境污染,对福建丛生小径竹进行了实验室模拟延伸改良连续蒸煮(EMCC)和常规硫酸盐法蒸煮(CKC)的研究。结果表明,EMCC蒸煮通过分段加入蒸煮药液和在逆流段进行药液置换,比CKC具有更高的脱木质素选择性。在蒸煮相同卡伯值的竹浆时,EMCC浆比常规硫酸盐浆(CK浆)具有更高细浆得率、较低粗渣率、更高粘度和更好强度性能。在相同的打浆度下,EMCC浆抗张指数、耐破指数和撕裂指数都比常规硫酸盐浆高。     

Characterisation of pulp demethylation during chlorine dioxide bleaching

Summary The methoxyl loss from softwood kraft pulp during chlorine dioxide treatment can be accounted for by methanol and the methoxyl content of dissolved organic material in the bleach filtrate. This was established by a methoxyl group mass balance made at different bleaching times. It was found that ClO₂ rather than the in-situ generated hypochlorous acid is mainly responsible for the methanol formation. It was shown that fully methylated pulp is hardly demethylated by ClO₂ under industrial ClO₂ bleaching conditions when hypochlorous acid is effectively captured. Furthermore, the rates of formation of methanol and methoxyl group containing dissolved organic material are proportional to each other. The experimental evidence suggest that demethylation and delignification are closely related during ClO₂ treatment of softwood kraft pulp.     

Oxidative cleavage of lignin aromatics during chlorine bleaching of kraft pulp

Methanol liberation and methoxyl loss during chlorine bleaching of softwood kraft pulp were quantitatively investigated to estimate the degree of structural modification of lignin aromatics. An increase in the chlorine multiple led to enhanced methoxyl loss from lignin. Our result, using pH-adjusted chlorine water (pH 5.7), by which chlorination under oxidation-favorable conditions was achieved, strongly supported the importance of the oxidation reaction by chlorine during delignification and lignin degradation. It was also suggested that methanol can be produced not only via catalytic hydrolysis by chlorine but via oxidative cleavage of the ether bond as well. The infrared spectrum of chlorolignins suggested that chlorine oxidation can open aromatic rings to muconic acid derivatives without cleaving ether bonding of the methoxyl group. No straight relation between the methoxyl content and the kappa number of chlorinated pulps was shown. The methoxyl content of bleached kraft pulps subjected to successive chlorination and alkali extraction showed a good relation with the kappa number. This means that almost all the portions of the oxidatively modified lignin structure were successfully removed during these treatments, and the aromatic structures of residual lignin in chlorinated and alkali-extracted pulps were thought to remain intact.Part of this paper was presented at the 46th Annual Meeting of the Japan Wood Research Society, Kumamoto, April 1996; the 10th International Symposium on Wood and Pulping Chemistry, Yokohama, June 1999; and the 67th Pulp and Paper Research Conference, Tokyo, June 2000     

Acetic acid pulping of wheat straw under atmospheric pressure

Atmospheric acetic acid pulping of wheat straw was carried out. Pulping conditions and their effects on pulp properties were investigated in detail, and a comparison between acetic acid (AcOH) pulp and soda-anthraquinone (AQ) pulps of wheat straw was made of the chemical composition, strength, and fiber morphology of the pulps. Wheat straw was successfully pulped and fractionated into pulp (cellulose), acetic acid lignin, and sugars (monosaccharides from hemicellulose), making it easy to utilize them. It was found that among the pulping conditions the dosage of H₂SO₄ as catalyst was the most notable, and the extent and rate of delignification could be controlled by varying the amount of the catalyst. The results also showed that acetic acid pulp was quite different from soda-AQ pulp. About 70% of the ash or 90% of the silica in wheat straw were kept in AcOH pulp. The ash might function as filler and be beneficial to the printability of paper. It was known that many epidermal cells existed in AcOH pulp in bundles or in single cells. These ash-rich nonfiber cells seemed to hinder the bonding between fibers. AcOH pulp had lower strength than soda-AQ pulp, which might result mainly from the chemical damage of fibers caused by acid, not from the depolymerization of cellulose.Part of this paper was presented at the 65th Pulp and Paper Research Conference of Japan TAPPI, Tokyo, June 1998     

Empirical modeling of chlorine dioxide delignification of oxygen-delignified hardwood kraft pulp

Due to the complexity of delignification, it is still not accurate enough to describe the whole chlorine dioxide delignification system with mechanistic models such as kinetic studies. The simple aim of predicting and optimizing the process requires the use of economical empirical models, few of which are in the literature. In this study, principal component analysis was used to classify various bleaching response variables, including end pH, kappa number, viscosity, and optical properties such as brightness, into different categories. Statistical methods, including factorial design, multiple regression, and response surface methodology, were then used successfully to screen the importance of bleaching factors and their interactions. Models to control, predicate, and optimize the bleaching responses were established. In most cases, the results of empirical modeling coincided well with those from conventional research methods, but the empirical methodology was more economic or less laborious. The empirical models are robust enough to predicate and optimize the bleaching responses to chlorine dioxide delignification of oxygen-delignified hardwood kraft pulp.     

Residual extractives in aspen kraft pulps and their impact on kappa number and Klason lignin determination

We investigated the impact of residual extractives on lignin determination by lignin content difference between unextracted and extracted pulps, residual extractives analysis, and lignin content contribution from model extractive compounds. There were two different kinds of extractives in aspen kraft pulp. The extractives impacting on kappa number determination were well removed in oxygen delignification; these were mainly unsaturated fatty acids. However, the extractives impacting on Klason lignin determination were largely resistant to oxygen delignification; these were mainly saturated fatty acids, sterols, and hydrocarbons. Oxidation of unsaturated fatty acids was the main reaction in oxygen delignification. These trends were confirmed by simulation of lignin content determination with three model extractive compounds (β-sitosterol, linoleic acid, and palmitic acid). The publication of this article was made possible by an Emachu Research Fund. The authors are grateful for the fund.     

中国引种澳大利亚相思树种制硫酸盐浆适应性研究

无论是从林业角度还是在制浆性能方面，不同种源间存在明显差异。本文研究了我国亚热带工区引种澳大利亚相思树的基本密度纸浆产率、制硫酸盐浆和漂白性能，比较了不同种源间的差异。研究结果表明，在有效碱用量为１２．５％－１５．５％时纸浆得率达５１．２％－５３．６％，经ＣＥＨＤ四段漂白后，所得纸浆性能可以满足配抄印刷和包装类用纸要求。     

杨木制浆技术的新进展

本文介绍了用杨木生产漂白化学浆,包括硫酸盐法,硫酸盐-蒽醌法,烧碱-蒽醌法和碱性亚硫酸钠-蒽醌法制浆;用杨木生产漂白化学热磨机械浆;用杨木生产碱性过氧化氢机械浆;特别是杨木碱性过氧化氢机械浆是90年代发展研制成功的高得率、高白度和强度性好的新化学机械浆种,它适用于配抄低定量胶印新闻纸、低定量涂布纸等。     

Studies on the effect of prehydrolysis and amine in cooking liquor on producing dissolving pulp from jute (Corchorus capsularis)

Dissolving pulps are the raw materials for the production of many different end-products. Jute is a very good source of cellulose. In this investigation, jute fiber was subjected to pulping in soda process in order to produce dissolving pulp under different prehydrolysis conditions and compared with prehydrolysed kraft pulp from jute. An increase of the prehydrolysis temperature or H₂SO₄ in prehydrolysis liquor increased the α-cellulose content and decreased the viscosity of pulp. The effect of ethylenediamine in soda liquor was also investigated when producing dissolving pulp. Jute fiber produced pulp having 90–97% α-cellulose. Ethylenediamine in soda liquor produced pulp of higher yield, viscosity and higher α-cellulose content than that of prehydrolysis soda or kraft pulp. The α-cellulose content and viscosity were increased with the increase of amine in soda liquor. The kappa number of dissolving pulp from jute was very low (9–5), which indicated that less bleaching chemicals are required for bleaching. The bleachability of soda-ethylenediamine pulp was lower than prehydrolysed soda and kraft pulp in ECF bleaching sequences. The bleachability of soda-ethylenediamine pulp was improved at the sacrifice of pulp yield when prehydrolysis was done prior to pulping. The alkali solubility S ₁₀ and S ₁₈ were 4–9 and 2–4%, respectively.     

TCF Bleaching of Populus tomentosa Kraft Pulps with H2O2 Pretreatment under Acid Condition

The process of peroxide bleaching of Populus tomentosa kraft pulp with H2O2 pretreatment under acid condition was studied. The variations of pulp characteristics such as brightness, Kappa number and viscosity during the peroxide bleaching process were discussed and the concept of the A/B value was presented for the first time. The results show that acid pretreatment with H2O2 is essential to improve pulp brightness and avoid viscosity loss. The conclusion is reached that the A/B value has great influence on pulp properties when the total amount of peroxide used in the bleaching process is 2%–5%. Pulp with a high viscosity and brightness can be obtained when A/B is about 0.15.     

Sulfuric acid bleaching of kraft pulp III: reactivity of kraft pulping-resistant structures under acidic conditions

To investigate the bleaching mechanism, a lignincarbohydrate complex (LCC) model compound, a vinyl ether-type lignin model dimer, and a hexeneuronic acid model compound were treated with dilute sulfuric acid of different pHs. Beech kraft pulp and red pine kraft pulp were also treated with dilute sulfuric acid and then extracted with aqueous alkali. The amount of hexeneuronic acid degradation products in acid effluents and lignin dissolved in alkali effluents were determined. It was found that the benzyl ether-type LCC bond and the vinyl ether bond in lignin were effectively cleaved under the pH where sulfuric acid bleaching of kraft pulp was effective. Hexeneuronic acid group was also effectively degraded during sulfuric acid bleaching. In beech kraft pulp bleaching, both lignin removal and hexeneuronic acid removal contributed to the kappa number reduction. In red pine bleaching, the contribution of hexeneuronic acid removal was negligible, and most of the kappa number reduction was achieved by the lignin removal.Part of this report was presented at the 9th International Symposium on Wood and Pulping Chemistry, Montreal, July 1997     

世界木材制浆技术新进展

文章论述了木材制浆技术的新进展，在硫酸盐法制浆技术的革新方面，推荐了间歇蒸煮的快速置换加热（ＲＤＨ）技术与连续蒸煮的改良连续蒸煮（ＭＣＣ）和深度脱木素改良连续蒸煮（ＥＭＣＣ）技术。还介绍了超高得率制浆方法，特别是碱性过氧化氢机械制浆（ＡＰＭＰ）法和爆破制浆（ＥＰ）法，用这两种方法生产的纸浆得率高、白度高、强度高、能耗较低。     

麦草碱性亚硫酸盐制浆生物炼制的研究(I) ——深度脱木质素及木质素磺化特性

提出了非木材木质纤维生物质碱性亚硫酸盐制浆(ASP)生物炼制的理念,研究了总用碱量、亚硫酸化度、温度和时间对麦草碱性亚硫酸盐法蒸煮深度脱木质素特性和木质素磺化的影响。结果表明:麦草ASP法具有高的深度脱木质素选择性;深度脱木质素延伸与木质素磺化度提高具有一致性;总用碱量、亚硫酸化度、最高温度和保温时间对深度脱木质素选择性和木质素磺化度都有重要的影响;在总碱用量18.0%,亚硫酸化度85.0%,液比值3.5,最高温度168℃,保温150 min的条件下,可制得卡伯值8.8,得率56.8%,黏度为33.3 mPa.s的优良纸浆,此时黑液中磺化木质素磺酸基含量达2.16 mmol/g(以固形物计)。从深度脱木质素选择性、木质素磺化和纸浆基本特性考虑,麦草ASP法具有制浆生物炼制的前景。     

Performance of new and commercial xylanases for ECF and TCF bleaching of eucalyptus kraft pulp

Since xylanases can differ widely in their bleaching efficiency, the performance of one new and two commercial xylanases was evaluated in an eucalyptus kraft pulp following XD (X: xylanase; D: chlorine dioxide) and XP (P: hydrogen peroxide) sequences. The new xylanase did not show a significant bleach boosting effect but increased the hexenuronic acid (HexA) removal by 10% after the D stage. The two commercial xylanases behaved in a different way, being one of them (X_C) the most effective in increasing delignification (9%) and brightness (3%ISO). Its effectiveness was related to its greater action on releasing the xylan polymer, thus producing also a strong decrease in the HexA contents during the enzymatic stage (15%). All xylanases produced morphological changes in the fibre surfaces, but only with X_C cracks and holes that improved the diffusion of reactives were observed. Finally, the best bleaching results were obtained with the XD sequence and therefore, a complete bleaching sequence XDEopD₁ (Eop: alkaline extraction with oxygen and peroxide) was carried out with the best enzyme.